Pesticidal pyrazoles and derivatives

ABSTRACT

Process of protection of building already built or going to be built, whereby an effective amount of insecticidally active amount of compound is spread around or under the said building at discrete locations. The insecticide may be an arylpyrazole.

[0001] An object of the instant invention is to protect building alreadybuilt or going to be built against crawling insect, especially againsttermites.

[0002] The insecticidal compounds of the family of the 1-arylpyrazolesare known to be active against termites.

[0003] Conventional termite control operators apply the chemical aroundor under the building or houses to form a barrier against termitesinvasion. However loopholes in the treatment may cause failure ofprotection of the houses.

[0004] Another system is to put a bait which contains- an attractant fortermites so as to force the termites to eat the bait and then to bekilled by the active ingredient contained also in that bait.

[0005] An object of the invention is to provide an improved process ofprotection of houses.

[0006] Another object of the invention is to provide a treatment againsttermites which reduce the number of the call-back from house owners oftreated houses.

[0007] An object of the instant invention is to protect the buildingwith the minimum amount of insecticidally active ingredient.

[0008] Another object of the instant invention is to have a good levelof protection of buildings against termites while reducing the amountof. applied insecticide.

[0009] Another object of the instant invention is to reduce the need totreat directly the location where the termites are or are expected tobe.

[0010] Another object of the instant invention is to provide a curativetreatment with reduced need to find out the precise place of termitesattacks.

[0011] Another object of the instant invention is to provide a curativetreatment which is effective even when attacked parts are untreated.

[0012] Another object of the instant invention is to provide a curativetreatment which is mainly a blind treatment with no checking of theattacked parts.

[0013] Another object of the instant invention is to provide a termitetreatment functioning like an intangible trap.

[0014] Another object of the instant invention is to provide a termitetreatment without barrier.

[0015] Another object of the instant invention is to provide a termitetreatment with is mainly a soil treatment.

[0016] It has been found that these goals may be achieved by mean of theprocess of the instant invention.

[0017] The present invention relates to a process of protection ofbuilding already built or going to be built, whereby an effective amountof insecticidally active amount of compound is spread around or underthe said building at discrete locations.

[0018] The insecticidally active material which can be used in theinvention is an active ingredient which is active by contact (contactwith species to be killed) and has no repellent effect on the insects,preferably no repellent effect on the insects to be killed.

[0019] A preferred class of active ingredient which can be used in theinvention are the compounds without quick knock-down effect, orcompounds able to produce a so-called secondary killing effect, that isto say an action of killing insects which have not been directly treatedby mean of the said insecticide. Also preferred are the insecticideswhich are able to kill the termites of the termites nest when broughtback by treated termites coming close to the house or building built orto be built.

[0020] In a practical point of view, the most preferred compounds areinsecticides of the 1-arylpyrazole type, especially those having theformula (I)

[0021] in which:

[0022] R₁ is CN or methyl or a halogen atom,

[0023] R₂ is S(O)_(n)R₃ or 4,5-dicyanoimidazol 2-yl or haloalkyl,

[0024] R₃ is alkyl or haloalkyl;

[0025] R₄ represents a hydrogen or halogen atom or a member of a groupconsisting of NR₅R₆, S(O)_(m)R₇, C(O)R₇, C(O)O-R₇, alkyl, haloalkyl, OR₈and—N═C(R₉)(R₁₀);

[0026] R₅ and R₆ independently represent the hydrogen atom or an alkyl,haloalkyl, C(O)alkyl, alkoxycarbonyl or S(O)_(r)CF₃ radical; or R₅ andR₆ can together form a divalent alkylene radical which can beinterrupted by one or two divalent heteroatoms, such as oxygen orsulfur;

[0027] R₇ represents an alkyl or haloalkyl radical;

[0028] R₈ represents an alkyl or haloalkyl radical or a hydrogen atom;

[0029] R₉ represents an alkyl radical or a hydrogen atom;

[0030] R₁₀ represents a phenyl or heteroaryl group which may optionallybe unsubstituted or substituted by one or more halogen atoms or a memberof the group consisting of OH, —O-alkyl, —S-alkyl, cyano, and alkyl;

[0031] R₁₁ and -R₁₂ represent, independently of one another, a hydrogenor halogen atom, or CN or NO₂,

[0032] R₁₃ represents a halogen atom or a haloalkyl, haloalkoxy,S(O)_(q)CF₃ or SF₅ group,

[0033] X represents a trivalent nitrogen atom or a C-R₁₂ radical, theother three valences of the carbon atom forming part of the aromaticring,

[0034] m, n, q, and r represent, independently of one another, aninteger equal to 0, 1, or 2,

[0035] provided that, when R₁₁ is methyl, then either R₃ is haloalkyl,R₄ is NH₂, R₁₁ is Cl, R₁₃ is CF₃ and X is N; or then R₂ is4,5-dicyanoimidazol 2-yl, R₄ is Cl, R₁₁ is Cl, R₁₃ is CF₃, and Xis=C-Cl.

[0036] Alkyl groups have generally 1 to 6 carbon atoms.

[0037] A preferred group of effective 1-arylpyrazoles of the presentinvention is that wherein:

[0038] R₁ is CN; R₃ is a haloalkyl radical; R₄ is NH₂; X is C-R₁₂;

[0039] R₁ and R₁₂ represent, independently of one another, a halogenatom; and

[0040] R₁₃ is a haloalkyl radical.

[0041] A most preferred compound is 5-amino 1-(2,6-dichloro4-trifluoromethyl phenyl) 4-trifluoromethylsulfinyl 3-cyanopyrazole,hereafter designated as compound (A).

[0042] Compounds of formula (I) may be prepared according to knownprocesses, for example as described in International Patent Publicationsn° WO 87/3781, 93/6089, and 94/21606 as well as in European PatentApplications 295117, 403300, 385809 or 679650. German Patent Publication19511269 and U.S. Pat. Nos. 5,232,940 and 5,236,938 or other processaccording to the knowledge of a man skilled in the art of chemicalsynthesis, which is deemed to include the Chemical Abstract and theliterature referred to therein. Compositions comprising the compounds offormula (I) may also be prepared according to the teaching of same priorart or similar one.

[0043] An advantageous way of practicing the invention is to use theactive ingredient in a formulation which does not contain any adjuvanthaving termite attractant properties. Even though, such attractant maybe used optionally, it may be risky, and it may make the residents orowners of the house reluctant against such treatment. Known processeswere generally unable to avoid the use of attractant in order to beeffective.

[0044] The process of the invention may be practiced in a preventive wayas well as in a curative way.

[0045] The actual treatment by mean of active ingredient may be madeinside or outside the outline of the houses or buildings to be built.

[0046] It is generally more effective to apply the active ingredient orformulation at a locus where the insects, especially the termites aremore frequently crawling or traveling or climbing. These locus are moreparticularly the corners and/or crossing walls of the buildings orbuildings which are going to be built. They are also more particularlythe locus which have a greater humidity level than the rest of theperimeter of the house.

[0047] The active ingredient is applied advantageously on soil. It mightbe simple surface treatment or also spraying, mixing, blending ordrenching of the soil with a formulation.

[0048] The effective amount of compound applied on soil is generallywithin the range of 0.05 g of active ingredient per m² of surface of thesoil to 0.0001 g/m². This range is given for the precise locus where theactive ingredient is applied.

[0049] As already said, the active ingredient is applied on discretelocus. The general rate of application is such that the treated part ofthe perimeter of the house is 0.5 to 7.5 treated meter per 10 meter ofglobal perimeter, the width of treated locus being in the range of 1 to50 cm, preferably 5 to 30 cm.

[0050] For their application, the compounds of the formula (I), orderivatives thereof, are generally in the form of compositions, whichare in various solid or liquid forms.

[0051] Solid forms of compositions which can be used are dusting powders(with a content of the compound of formula (I), or a pesticidallyacceptable salt thereof, ranging up to 80%), wettable powders orgranules (including water dispersible granules), particularly thoseobtained by extrusion, compacting, impregnation of a granular carrier,or granulation starting from a powder (the content of the compound offormula (I), or a pesticidally acceptable salt thereof, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogenous or heterogeneous compositions containing one or morecompounds of formula (I), or pesticidally acceptable salts thereof, forexample granules, pellets, briquettes or capsules, maybe used to treatstanding or running water over a period of time. A similar effect may beachieved using trickle or intermittent feeds of water dispersibleconcentrates as described herein.

[0052] Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

[0053] Liquid compositions, for example, in the form of emulsifiable orsoluble concentrates most frequently comprise about 5 to about 80% byweight of the active ingredient, while the emulsions or solutions whichare ready for application contain, in their case, about 0.01 to about20% of the active ingredient. Besides the solvent, the emulsifiable orsoluble concentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilisers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, may be obtained from these concentrates by dilutionwith water. These compositions are included within the scope of thecompositions which may be employed in the present invention. Theemulsions may be in the form of water-in-oil or oil-in-water type andthey may have a thick consistency.

[0054] The liquid compositions of this invention may, in addition tonormal agricultural use applications be used for example to treatsubstrates or sites infested or liable to infestation by arthropods (orother pests controlled by compounds of this invention) includingpremises, outdoor or indoor storage or processing areas, containers orequipment for standing or running water.

[0055] All these aqueous dispersions or emulsions or spraying mixturescan be applied, by any suitable means, chiefly by spraying, at rateswhich are generally of the order of about 100 to about 1,200 liters ofspraying mixture per hectare, but may be higher or lower (e.g. low orultra-low volume) depending upon the need or application technique.

[0056] The concentrated suspensions, which can be applied by spraying,no are prepared so as to produce a stable fluid product which does notsettle (fine grinding) and usually contain from about 10 to about 75% byweight of active ingredient, from about 0.5 to about 30% of surfaceactive agents, from about 0.1 to about 10% of thixotropic agents, fromabout 0 to about 30% of suitable additives, such anti-foaming agents,corrosion inhibitors, stabilisers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

[0057] The wettable powders (or powder for spraying) are usuallyprepared so that they contain from about 10 to about 80% by weight ofactive ingredient, from about 20 to about 90% of a solid carrier, fromabout 0 to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilisers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient(s) is(are) thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is(are) ground using a mill or other suitablegrinder. This produces wettable powders, the wettability and thesuspendability of which are advantageous. They may be suspended in waterto give any desired concentration and this suspension can be employedvery advantageously for application.

[0058] The “water dispersible granules (WG)” (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

[0059] Generally speaking, the compositions for application againstpests usually contain from about 0.00001% to about 95%, moreparticularly from about 0.0005% to about 50% by weight of one or morecompounds of formula (I), or pesticidally acceptable salts thereof, orof total active ingredients

[0060] The following examples are given to help the man skilled in theart to understand how to practice the invention. It should not be usedto restrict or limit the said invention.

EXAMPLE 1

[0061] In an area where termites are passing or traveling, plans for ahouse are made. The plans are that the house will have a rectangularshape of 15 m×10 m with 4 rooms at the lower level.

[0062] Compound (A) is actually put on the soil at a rate of 0.01 g/m²of the soil at the location of the future corners of the house and atthe crossing of the walls corresponding to each room according to thefollowing scheme:

[0063] The treated area represents 5 m per 10 m of perimeter.

[0064] After 1 year after building the house, no attack of termite isobserved.

[0065] A similar experiment made with chlorpyrifos let the observation(one year after building the house) of a strong attack of termite (partsof the walls have hole of more than 10% of the volume).

EXAMPLE 2

[0066] Example 1 is repeated, except that the active ingredient isapplied inside the perimeter of the house. In other words, the locus ofapplication differ from example 1 only by the fact that it is located atthe other side of the wall. Results similar to those of example 1 areobtained.

1. Process of protection of building already built or going to be built,whereby an effective amount of insecticidally active amount of compoundis spread around or under the said building at discrete locations. 2.Process according to claim 1 wherein the active ingredient is aninsecticide with contact effect, and no repellent action against theinsects
 3. Process according to any of the foregoing claims wherein theactive ingredient has no quick knock down effect.
 4. Process accordingto claim 1 wherein the active ingredient is an insecticide with asecondary killing action
 5. Process according to any of the foregoingclaims wherein the active ingredient is all insecticide which is able tokill the termites of the nest when brought back by termites coiningclose to the house or building to be built
 6. Process according to anyof the foregoing claims wherein the active ingredient is an insecticideof the 1-arylpyrazole type
 7. Process according to any of the foregoingclaims wherein the active ingredient is an insecticide of the formula(I)

in which: R₁ is CN or methyl or a halogen atom, R₂ is S(O)_(n)R₃ or4,5-dicyanoimidazol 2-yl or haloalkyl, R₃ is alkyl or haloalkyl, R₄represents a hydrogen or halogen atom or a member of a group consistingof NR₅R₆, S(O)_(m)R₇, C(O)R₇, C(O)O—R₇, alkyl, haloalkyl, OR₈ and—N═C(R₉)(R₁₀); R₅ and R₆ independently represent the hydrogen atom or analkyl. haloalkyl, C(O)alkyl, alkoxycarbonyl or S(O)_(r)CF₃ radical; orR₅ and R₆ can together form a divalent alkylene radical which can beinterrupted by one or two divalent heteroatoms, such as oxygen orsulfur; R₇ represents an alkyl or haloalkyl radical; R₈ represents analkyl or haloalkyl radical or a hydrogen atom; R₉ represents an alkylradical or a hydrogen atom; R₁₀ represents a phenyl or heteroaryl groupwhich may optionally be unsubstituted or substituted by one or morehalogen is atoms or a member of the group consisting of OH, —O-alkyl,—S-alkyl, cyano, and alkyl; R₁₁ and R₁₂ represent, independently of oneanother, a hydrogen or halogen atom, or CN or NO₂, R₁₃ represents ahalogen atom or a haloalkyl, haloalkoxy, S(O)_(q)CF₃ or SF₅ group, Xrepresents a trivalent nitrogen atom or a C—R₁₂ radical, the other threevalences of the carbon atom forming part of the aromatic ring, m, n,q,.and r represent, independently of one another, an integer equal to 0,1, or 2, provided that, when R₁ is methyl, then either R₃ is haloalkyl,R₄ is NH₂, R₁₁ is Cl, R₁₃ is CF₃ and X is N; or then R₂ is4,5-dicyanoimidazol 2-yl, R₄ is Cl, R₁₁ is Cl, R₁₃ is CF₃, and Xis=C—Cl.
 8. Process according to any of the foregoing claims wherein theactive ingredient is an insecticide of the formula (I) wherein; R₁ isCN; R₃ is a haloalkyl radical; R₄ is NH₂; X is C—R₁₂; R₁₁ and R₁₂represent, independently of one another, a halogen atom; and R₁₃ is ahaloalkyl radical.
 9. Process according to any of the foregoing claimswherein the active ingredient is 5-amino 1-(2,6-dichloro4-trifluoromethyl phenyl) 4-trifluoromethylsulfinyl 3-cyanopyrazole. 10.Process according to any of the foregoing claims wherein the activeingredient is used in a composition which do not contain any attractantfor termite
 11. Process according to any of the foregoing claims whenused in a preventive way.
 12. Process according to any of the foregoingclaims when used in a curative way.
 13. Process according to any of theforegoing claims wherein the treatment is made by application to soil.14. Process according to claim 13 wherein the treatment is made byspraying or mixing.
 15. Process according to any of the foregoing claimswherein the treated locations are at comers and/or crossing walls of thebuilding or building which is going to be built.
 16. Process accordingto any of the foregoing claims wherein the treated locations are atplaces which have a greater humidity level than the rest of theperimeter of the house
 17. Process according to any of the foregoingclaims wherein the treated locations are inside the outline of the houseor building to be built
 18. Process according to any of the foregoingclaims wherein the treated locations are outside the outline of thehouse or building to be built
 19. Process according to any of theforegoing claims wherein the amount of active ingredient at the treatedlocations is within the range of 0.05 a.i. g/m² to 0.0001g/m²per surfaceof the soil
 20. Process according to any of the foregoing claims whereinthe discrete locations where the active ingredient is deposited arelocated in a such a way that the treated part of the perimeter of thehouse is 0.5 to 7.5 treated meter per 10 meter of global perimeter